Smokable substitute material and smoking products thereof

ABSTRACT

A smokable material designed to be used for cigars and cigarettes and having waterproof properties is disclosed. The material comprises a composition of a vinylene carbonate, the homopolymer or copolymers thereof, and a combustible filler, such as carbon, cellulose, cellulose derivatives or tobacco. The principal combustion products of the vinylene carbonate employed are carbon dioxide and water.

United States Patent [191 Briskin et al.

SMOKABLE SUBSTITUTE MATERIAL SMOKING PRODUCTS THEREOF Sutton ResearchCorporation, Los Angeles, Calif.

Filed: Ma 10, 1972 App]. No.: 252,003

Related US. Application Data Continuation-impart of Ser. No. 226,267,Feb. 14, 1972.

Assignee:

US. Cl 131/2, 131/17, l3l/l5 lint. Cl. A24b 3/14, A24b 13/00 Field ofSearch 131/2, 17, 140

[451 Aug. 27, 1974 [5 6] References Cited UNITED STATES PATENTS3,125,098 3/1964 Osborne l3l/l7R 3,545,448 12/1970 Mormon.... l3l/23,638,660 111972 Davis 131/2 Primary Examiner-Melvin D. Rein ABSTRACT Asmokable material designed to be used for cigars and cigarettes andhaving waterproof properties is dis closed. The material comprises acomposition of a vinylene carbonate, the homopolymer or copolymersthereof, and a combustible filler, such as carbon, cellulose, cellulosederivatives or tobacco. The principal combustion products of thevinylene carbonate employed are carbon dioxide and water.

14 Claims, No Drawings This is a continuation-in-part of our copendingapplication Ser. No. 226,267, filed Feb. 14, 1972, entitled SmokableMaterial and Smoking Products Thereof.

This invention relates to a smokable material and to smoking productsproduced with same.

Considerable effort has been and is currently being expended in thedevelopment of a smoking material as a substitute for tobacco. For themost part, such research and development has followed two directions. Inone direction, attempts have been made to replace tobacco withnon-tobacco vegetable products in which the leaves are dried, cured andshredded in the manner corresponding to that employed with tobaccoleaves. While such other vegetable products are generally free ofnicotine, they produce harsh smoking mixtures in which the smoke ischaracterized by undesirable levels of polycyclics and carbonyls. As aresult, such tobacco substitutes have not found ready acceptance as asmokable material in the manufacture of smoking products.

The other course which has been followed by research and development fora tobacco substitute is a reconstituted smoking product in whichnon-noxious inert or combustible fillers are combined with an organichinder or adhesive to form a sheet or product which can be used as afiller or wrapper in the manufacture of pipe tobacco, cigarettes orcigars. Representative of the binders that have been used are suchcellulosic materials as methyl cellulose, carboxymethyl cellulose (freeacid and sodium salt), and alginates, or natural gum such as guar gum,gum tragacanth, gum arabic, and locust bean gum and mixtures thereof.Such binders burn with such strong odors and acridity as to detract fromthe taste of the smoking product and undesirable amounts of chemicalirritants and carcinogens are found with the smoke that is formed.

it is an object of this invention to produce and to provide a method forproducing a smokable material which burns at a desired uniform slow ratewithout crackling and without flare while it is being smoked; whichremains lit between puffs on a cigar, cigarette, or pipe packedtherewith; which burns with an ash of sufficient strength, porosity andvolume to remain attached to the burning end of the cigar or cigaretteformed thereof; which does not give off undesirable or acrid odors ortaste while being smoked, and in which the amount of carcinogens andchemical irritants produced during smoking is materially reduced if notentirely eliminated.

This invention resides in the discovery that a smokable materialembodying many of the features described above can be produced withinert, noncombustible fillers and with combustible ingredients andmixtures thereof when embodied in combination with a synthetic polymericfilm forming material or binder in the formofa homopolymer l orcopolymer of vinylene carbonate (2) or vinyl carbonate derivative (3) orhydroxy (4), or ketone (5) derivative thereof.

['51s Hf] H HRi R,

in which R and R may each be hydrogen, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec butyl, pentyl, isopentyl, hexyl, nonyl, decyll orother alkyl group or mixtures of such hydrogen and alkyl groups.

Such polymers of vinylene'carbonate and derivatives thereof form waterinsoluble plastic films or coatings and can therefore function admirablyas a binder or' film former in the preparation of reconstituted smokableproducts when combined with inert noncombustible fillers and/orcombustible materials of the types previously described. The polymer (1)which consists of repeating 1,3-dioxolane-2-one ring system, in whichthe repeating units are coupled at the C and C positions, respectively,is capable of clean combustion to carbon dioxide and water, since allcarbon atoms in the ring system are bonded to oxygen atoms. The linearpolycarbonates should also burn in an analogous manner to yiels verylittle if any chemical irritants and carcinogens.

Polyvinylene carbonate can be produced by homopolymerization of vinylenecarbonate by the process described by M. S. Newman and R. W. Addor, J.Am. Chem. Soc., 75, 1263 (1953). The polymcthylol derivative can beproduced by hydrolysis of polyvinylene carbonate, as described by Unrulhand Smith, J. Org. Chem, 23, 625 (1958) and the corresponding ketoneshould be produced by conventional oxidation of the polymethylol.

Vinylene carbonate or derivatives thereof, copolymerized with olefins,such as acrylic acid, alkyl acrylates such as methyl acrylate or methylmethacrylate, or maleic acid or anhydride can be used as the film formeror binder in thesame manner as the polyvinylene carbonate, since suchcopolymers should also combust with the production of very little, ifany, noxious combustion products in the smoke.

Representative of inert, non-combustible fillers which may be used withthe polyvinylene carbonate or derivative or copolymer thereof, in themanufacture of a smokable product of the invention, are perlite, talc,diatomaeeous earth, titanium dioxide, silica and alumina, and mixturesthereof. Combustible ingredients which may be employed in themanufacture of smok-. able products of this invention are represented bycharcoal or other form of carbon, cellulose, oxycellulose, non-noxiouscellulose derivatives, degraded cellulose, non-noxious degradedcellulosic derivatives, nonnicotine vegetable products, and tobacco andmixtures thereof.

A smokable reconstituted material can be prepared of the describedingredients in a number of ways. For example, the inert filler and/orcombustible material can be admixed with the polymeric component andmasticated to form a smokable material for use as a packing for pipes,or for use as a filler in the manufacture of cigars and cigarettes.Reconstituted sheets can be formed of such materials by casting ormolding the mixture to sheet form or by taking the polymeric materialinto solution for admixture with the tiller or combustible ingredient tobe cast or otherwise formed into sheets. Reconstituted sheets can alsobe prepared by coating a film of the polyvinylene carbonate or the likepolymeric material with the filler and/or combustible material to form acomposite sheet product. The above reconstituted sheets ormaterialformed thereof can be subjected to heat treatment at anytemperature such as from 100C to 250C. Such heat treatment will operatefurther to reduce, if desired, chemical irritants produced uponcombustion of the smoking material.

In addition, because of the water insolubility of the polymericmaterial, conventional tobacco can be coated or impregnated withsolutions of the polymeric material, as by dipping or spraying, toprovide a protective coating which operates to retain the mixture andincrease the strength of the tobacco product without interfering withits aroma or taste.

Reconstituted sheets of the type described can be reduced to shreds orpellets for use as a packing for pipes, or as an internal filler forcigars or cigarettes. In addition, they can be used in sheet form ascover sheets or wrappers in the manufacture of cigars or cigaretteswherein the tiller comprises the smokable product of this invention or aconventional tobacco product.

In the manufacture of a smokable product, in accordance with thepractice of this invention, the polyvinylene carbonate, or derivative orcopolymer thereof, is employed in an amount which may range from l-l00percent, when used as a wrapper, to 2-10 percent by weight when used asa binder or film former in which the remainder is made up of the inertfiller and/or combustible material, as heretofore described. Variousadditions for the generation of smoke, aroma and taste and varioushumidifiers may be added, preferably in amounts which would not exceedl3 percent by weight of the smokable material. In many instances, itwill be desirable to add nicotine for aroma and taste in amounts which.will not exceed the amount of nicotine present in conventional tobacco.

Having described the basic concepts of this invention, the followingexamples are given by way of illustration, but not by way of limitation,of the practice of this invention:

EXAMPLE 1 A mixture consisting of 90 percent by weight of finely dividedtobacco and percent by weight of polyvinylene carbonate, dissolved inacetone. is poured onto a Teflon coated surface and allowed to air dry.The resulting reconstituted tobacco sheet can be processed and utilizedin sheet form as a wrapper for cigarettes or cigars or it can be-shredded for use as a filler in pipes, cigars or cigarettes.

EXAMPLE 2 A mixture of 33.5 percent by weight ofa non-noxiouscombustible filler (charred oxycellulose), 30 percent by weight ofcalcium carbonate, 10 percent by weight of magnesium carbonate, 1.5percent by weight of Rubidium oxalate and 25 percent by weight ofpolyvinylene carbonate, dissolved in acetone, is poured onto a Teflonsurface and allowed to air dry. The resulting reconstituted non-tobaccosheet can be utilized in sheet form as a wrapper for cigars orcigarettes, or it can be shredded for use as a filler for pipes,cigarettes or cigars.

Instead of polyvinylene carbonate in Example 2, use can be made ofpolyvinylene ketone or copolymers of vinylene carbonate and methylacrylate or methyl methacrylate, or maleic acid or anhydride inequivalent amounts to produce a smokable product.

Another important concept of this invention resides in means forimparting a desired coloration to the smokable material prepared inaccordance with the practice of this invention and to other smokablematerials of synthetic or natural origin, to provide the color andappearance of a fully cured tobacco or other desirable brownish color,without, at the same time, undesirably adding to the amount of smoke,odor, taste or acridity produced upon combustion.

In the past, use has been made of aniline based materials as coloringagents, but such materials are obnoxious upon combustion. Moregenerally, usage has been made of carmelized sugars or carbohydrates,but the combustion products produced therefrom are of an irritatingnature.

It has been found, in accordance with the further practice of thisinvention, that the desired coloration of the smokable material can beeasily and quickly developed by the use of the compound identified ascyclohexanehexone having the general formula The compound produces acolored reaction product with basic materials, preferably in thepresence of humidity, water or other solvent, in which the colors rangefrom orange to a very dark brown, depending somewhat upon the strengthof the base, the concentration of the compound and the temperature towhich the material is heated for color development, together orseparately. Such basic materials are present or can be added to thesmokable material of synthetic or natural origin. Heat accelerates colordevelopment but it is undesirable to exceed a temperature of C and it ispreferred to heat the treated material to a temperature below about60-70C for a short period ot time.

The compound can be sprayed onto or otherwise incorporated in thesmokable material of synthetic or natural origin. It can be used intrace amounts to give an improved appearance to the smokable material,but it is preferred to employ the compound in an amount within the rangeof 0.01 to 1.0 percent by weight of the smokable material.

Upon combustion, the coloring agent does not give off any significantamount of smoke, odor, aroma, or taste and therefore does not interferewith the pleasure of smoking the smokable material.

EXAMPLE 3 The composition of Example 1 is formulated to contain 0.1percent by weight of cyclohexanehexone before pouring onto the Tefloncoated surface for sheeting. The sheet is then heated for a short periodof time of about 10 minutes to 50C.

' EXAMPLE 4 The shredded filler .produced in Example 2 is spray coatedwith 0.05 percent by weight of cyclohexanehexone and heated for 10-20minutes ata temperature of EXAMPLE 5 The procedure of Example 4 isrepeated with shreds of cured natural tobacco, instead of the syntheticmaterial of Example 2. The natural tobacco takes on an attractive deepbrown color of the highest quality cured tobacco.

It will be understood that changes may be made in the details offormulation and operation without departing from the spirit of theinvention, especially as defined in the following claims.

We claim:

1. A smokable material comprising the mixture of a resinous binderselected from the group consisting of vinylene carbonate or thehomopolymer of copolymers thereof from which the combustion products areprimarily carbon dioxide and water, and in which the vinylene carbonatehas the general formula in which R, and R are selected from the groupconsisting of hydrogen and an organic alkyl group and mixtures thereof,and a combustible filler selected from the group consisting of charcoal,combustible carbon, cellulose, oxycellulose, non-noxious cellulosederivative, degraded cellulose, non-noxious degraded cellulosederivative, vegetable products and tobacco and mixtures thereof.

2. A smokable material as claimed in claim 1 which includes anon-combustible filler selected from the group consisting of perlite,talc, diatomaceous earth, titanium dioxide, silica and alumina andmixtures thereof.

3. A smokable material as claimed in claim 1 in which the smokablematerial is in the form of a reconstituted sheet formed of the resinousbinder in admixture with the filler.

4. A smokable material as claimed in claim 1 in which the smokablematerial is in the form of a reconstituted sheet formed of a film of theresinous binder and a layer of filler bonded to the surface of the film.

5. A smokable material as claimed in claim 1 in which the smokablematerial is a tobacco product coated and impregnated with a resinousbinder component.

6. A wrapper for cigars and cigarettes comprising a sheet formed of thesmokable material of claim-l.

7. A filler for pipes, cigars and cigarettes comprising shreds of thesmokable material of claim 1.

8. A cigarette comprising a wrapper formed of a combustible material anda filler within the wrapper of the smokable material of claim 1 reducedto shreds.

9. A cigarette as claimed in claim 8 in which the wrapper is formed ofthe smokable material of claim 1.

10. A cigar comprising a wrapper of a combustible material and a fillerwithin the wrapper formed of sheets of the smokable material of claim 1.

11. A cigar as claimed in claim 10 in which the wrapper is areconstituted sheet of the smokable material of claim 1.

12. The method as claimed in claim 1 in which cyclohexanehexone isincorporated as a component of the mixture making up the smokablematerial.

13. A smokable material as claimed in claim 1 in which the smokablematerial has been subjected to a heat treatment at a temperature withinthe range of 14. A smokable material as claimed in claim 1 in whichchemical irritants present have been reduced by heat treatment of thesmokable material at a temperature within the range of l0O-250C for ashort period of time.

2. A smokable material as claimed in claim 1 which includes anon-combustible filler selected from the group consisting of perlite,talc, diatomaceous earth, titanium dioxide, silica and alumina andmixtures thereof.
 3. A smokable material as claimed in claim 1 in whichthe smokable material is in the form of a reconstituted sheet formed ofthe resinous binder in admixture with the filler.
 4. A smokable materialas claimed in claim 1 in which the smokable material is in the form of areconstituted sheet formed of a film of the resinous binder and a layerof filler bonded to the surface of the film.
 5. A smokable material asclaimed in claim 1 in which the smokable material is a tobacco productcoated and impregnated with a resinous binder component.
 6. A wrapperfor cigars and cigarettes comprising a sheet formed of the smokablematerial of claim
 1. 7. A filler for pipes, cigars and cigarettescomprising shreds of the smokable material of claim
 1. 8. A cigarettecomprising a wrapper formed of a combustible material and a fillerwithin the wrapper of the smokable material of claim 1 reduced toshreds.
 9. A cigarette as claimed in claim 8 in which the wrapper isformed of the smokable material of claim
 1. 10. A cigar comprising awrapper Of a combustible material and a filler within the wrapper formedof sheets of the smokable material of claim
 1. 11. A cigar as claimed inclaim 10 in which the wrapper is a reconstituted sheet of the smokablematerial of claim
 1. 12. The method as claimed in claim 1 in whichcyclohexanehexone is incorporated as a component of the mixture makingup the smokable material.
 13. A smokable material as claimed in claim 1in which the smokable material has been subjected to a heat treatment ata temperature within the range of 100*-250*C.
 14. A smokable material asclaimed in claim 1 in which chemical irritants present have been reducedby heat treatment of the smokable material at a temperature within therange of 100*-250*C for a short period of time.